JP6960386B2 - Manufacturing method of carbon nanotube molded body and carbon nanotube molded body manufacturing equipment - Google Patents

Description

The present invention relates to a technique for producing a carbon nanotube molded product.

In recent years, it has been proposed to mold a plurality of carbon nanotubes into various shapes and use them in various products such as electrodes or sensors. For example, Patent Document 1 proposes a technique for drawing out a sheet-shaped carbon nanotube web from a carbon nanotube array, which is an aggregate of carbon nanotubes erected on a substrate. In FIG. 2 of Patent Document 1, in order to pull out the carbon nanotube web 10 of a desired width from the carbon nanotube array 1, carbon is carbonized from the side opposite to the substrate 3 on both sides in the width direction of the region D where the carbon nanotube web 10 is to be pulled out. It is disclosed that the adhesive tape 20A that comes into contact with the nanotube array 1 is provided.

Further, in Patent Document 2, the carbon nanofibers are pulled out from the carbon nanofiber aggregate formed on the surface of the rotating cylindrical or columnar substrate while rotating (that is, twisting) by a drawing device such as a bobbin to conduct conductivity. Techniques for manufacturing wire have been proposed. In FIG. 3 of Patent Document 2, a technique of peeling the carbon nanofiber assembly B from the cylindrical substrate 10 by the guide portion 202 and then drawing out a conductive wire from the tip of the peeled carbon nanofiber assembly B. Is disclosed. In FIG. 3, the carbon nanofiber aggregate B is excessively pulled by the drawing device 81, and the entire carbon nanofiber aggregate B is in a tense state, and the carbon nanofiber aggregate B and the catalyst layer A being formed on the substrate 10 are in a tense state. The carbon nanofiber aggregate B that is peeled off from the substrate 10 and moves is sandwiched from above and below by the guide portion 202 and the regulating portion 203 in order to suppress the occurrence of peeling between the two, and the upward movement is restricted. Has been done.

International Publication No. 2017/200045 Japanese Unexamined Patent Publication No. 2014-237563

By the way, in the manufacturing apparatus of Patent Document 2, the tip end portion of the carbon nanofiber aggregate B (also referred to as carbon nanotube array) that is peeled off from the substrate 10 and moves is added from the friction with the guide portion 202 or from the drawing device 81. Due to tensile force or the like, the guide portion 202 and the regulating portion 203 may vibrate in the width direction (that is, in the direction perpendicular to the pulling direction and along the lower surface of the regulating portion 203), and it may be difficult to pull out stably. ..

The present invention has been made in view of the above problems, and an object of the present invention is to suppress vibration in the width direction of the carbon nanotube array during drawing.

The invention according to claim 1 is a method for manufacturing a carbon nanotube molded body, wherein a) a step of preparing a carbon nanotube array which is an assembly of carbon nanotubes erected on a substrate, and b) the carbon nanotube array The step of peeling from the substrate, c) the step of electrostatically adsorbing the carbon nanotube array peeled from the substrate by the adsorption portion, and d) the carbon nanotube array in a state of being electrostatically adsorbed on the adsorption portion. It includes a step of forming a carbon nanotube sheet by pulling it out.

The invention according to claim 2 is the method for manufacturing a carbon nanotube molded body according to claim 1, wherein in the step b), the release member is brought into contact with the joint portion between the carbon nanotube array and the substrate. By moving the peeling member relative to the substrate in this state, a peeling array portion which is a portion of the carbon nanotube array peeled from the substrate is formed, and a predetermined peeling array portion is formed with respect to the peeling member. In the step c), the peeling array portion during relative movement is electrostatically attracted by the suction portion arranged along the relative movement path of the peeling array portion. In step d), the carbon nanotube sheet is pulled out from the peeling array portion that is relatively moving in a state of being electrostatically adsorbed by the adsorption portion.

The invention according to claim 3 is the method for manufacturing a carbon nanotube molded product according to claim 2, wherein the drawing direction, which is the direction in which the carbon nanotube sheet is pulled out, is inclined with respect to the peeling portion moving direction. The direction.

The invention according to claim 4 is the method for producing a carbon nanotube molded product according to any one of claims 1 to 3, and e) the carbon nanotube sheet is placed in the width direction after the step d). It further comprises a step of forming a linear carbon nanotube wire by collecting in.

The invention according to claim 5 is the method for producing a carbon nanotube molded product according to claim 4, wherein the carbon nanotube wire is formed by twisting the carbon nanotube sheet in the step e).

The invention according to claim 6 is a carbon nanotube molded body manufacturing apparatus, wherein a substrate holding portion for holding a substrate on which a carbon nanotube array, which is an aggregate of carbon nanotubes, is erected, and the carbon nanotube array are mounted on the substrate. A carbon nanotube sheet is formed by pulling out a peeling mechanism for peeling, an adsorption portion for electrostatically adsorbing the carbon nanotube array peeled from the substrate, and the carbon nanotube array in a state of being electrostatically adsorbed on the adsorption portion. It is equipped with a pull-out mechanism.

The invention according to claim 7 is the carbon nanotube molded body manufacturing apparatus according to claim 6, wherein the peeling mechanism includes a peeling member that abuts at a joint portion between the carbon nanotube array and the substrate, and the peeling. By moving the member relative to the substrate, a peeling array portion, which is a portion of the carbon nanotube array that has been peeled from the substrate, is formed, and the peeling array portion is designated with respect to the peeling member. The suction portion is arranged along the relative movement path of the peeling array portion, and electrostatically attracts the peeling array portion during relative movement. The pull-out mechanism pulls out the carbon nanotube sheet from the peeling array portion which is relatively moving in a state of being electrostatically attracted by the suction portion.

The invention according to claim 8 is the carbon nanotube molded product manufacturing apparatus according to claim 7, wherein the drawing direction, which is the direction in which the carbon nanotube sheet is pulled out, is a direction inclined with respect to the peeling portion moving direction. Is.

The invention according to claim 9 is the carbon nanotube molded body manufacturing apparatus according to claim 7 or 8, which is arranged along the relative movement path of the peeling array portion and rotates perpendicular to the relative movement path. A guide portion for guiding the peeling array portion while rotating about the shaft is further provided, and the suction portion is arranged at a position facing the guide portion with the peeling array portion interposed therebetween.

The invention according to claim 10 is the carbon nanotube molded body manufacturing apparatus according to claim 7 or 8, wherein the suction portion rotates about a rotation axis perpendicular to the relative movement path and the peeling array. It is a guide part that guides the part.

The invention according to claim 11 is the carbon nanotube molded body manufacturing apparatus according to any one of claims 6 to 10, wherein the carbon nanotube sheets are collected in the width direction to form a linear carbon nanotube wire. A wire forming portion for forming the above is further provided.

The invention according to claim 12 is the carbon nanotube molded body manufacturing apparatus according to claim 11, and the wire forming portion forms the carbon nanotube wire by twisting the carbon nanotube sheet.

In the present invention, vibration in the width direction of the carbon nanotube array at the time of drawing can be suppressed.

It is a side view of the molded article manufacturing apparatus which concerns on 1st Embodiment. It is a top view of the molded body manufacturing apparatus. It is a figure which shows the relationship between the bulk density and the thickness of a carbon nanotube array. It is a front view of a guide part and a suction part. It is a figure which shows the flow of manufacturing of the carbon nanotube molded article. It is a side view of the molded article manufacturing apparatus which concerns on 2nd Embodiment. It is a front view of a guide part. It is a side view of the molded article manufacturing apparatus which concerns on 3rd Embodiment. It is a figure which shows another example of manufacturing of the carbon nanotube molded article.

FIG. 1 is a side view showing a carbon nanotube molded body manufacturing apparatus 1 (hereinafter, also simply referred to as “molded article manufacturing apparatus 1”) according to the first embodiment of the present invention. FIG. 2 is a plan view showing a molded product manufacturing apparatus 1. In the examples shown in FIGS. 1 and 2, the molded product manufacturing apparatus 1 has a sheet-like (so-called web-like) carbon nanotube sheet formed of a plurality of carbon nanotubes (CNTs) and a linear (so-called thread-like) sheet. The carbon nanotube wire of the above is manufactured as a carbon nanotube molded body. In the following description, the upper side and the lower side in FIG. 1 are simply referred to as "upper side" and "lower side". The vertical direction in FIG. 1 does not necessarily have to coincide with the direction of gravity.

The molded body manufacturing apparatus 1 includes a substrate holding portion 21, a peeling member 22, a moving mechanism 23, a guide portion 24, a wire forming portion 25, a drawing mechanism 26, and a suction portion 61. In FIG. 2, in order to facilitate the understanding of the figure, only the outline of the suction portion 61 is shown by a chain double-dashed line. The moving mechanism 23 includes a substrate take-up roll 231 and a rotating mechanism 232. The pull-out mechanism 26 includes a molded body take-up roll 261 and a rotation mechanism 262. The rotation mechanisms 232 and 262 are, for example, electric motors, respectively.

The substrate holding portion 21 holds the substrate 92 on which the carbon nanotube array 91, which is an aggregate of a large number of carbon nanotubes, stands. The substrate 92 is, for example, a long thin plate-like member having flexibility. The substrate 92 is, for example, a silicon substrate or a stainless steel substrate provided with a silicon dioxide film or the like on the surface. The carbon nanotube array 91 is formed by growing a large number of carbon nanotubes oriented substantially perpendicular to the surface 921 of the substrate 92 on the substrate 92 by, for example, a chemical vapor deposition method (that is, a CVD method). .. The formation of the carbon nanotube array 91 may be performed by various other methods.

The thickness of the carbon nanotube array 91 (that is, the length of the carbon nanotubes contained in the carbon nanotube array 91 in the vertical direction) is, for example, 50 μm to 1000 μm. In the present embodiment, the thickness of the carbon nanotube array 91 is 50 μm to 500 μm. The thickness of the carbon nanotube array 91 is measured by, for example, a scanning electron microscope (SEM) (manufactured by JEOL Ltd.) or a non-contact film thickness meter (manufactured by KEYENCE CORPORATION).

In the carbon nanotube array 91, for example, there are 10 ^{nine 10 11} pieces of carbon nanotubes per 1 cm ^2. The distance between adjacent carbon nanotubes is, for example, 100 nm to 200 nm. The outer diameter of each carbon nanotube is, for example, 10 nm to 30 nm. Each carbon nanotube is, for example, a multi-walled carbon nanotube having 5 to 10 layers. Each carbon nanotube may be a multi-walled carbon nanotube having 4 layers or less or 11 layers or more, or may be a single-walled carbon nanotube.

The bulk density of the carbon nanotube array 91 is, for ^{example, 10mg / cm 3 ~60mg / cm 3} . Preferably, the bulk density of the carbon nanotube array 91 ^{is 20mg / cm 3 ~50mg / cm 3} . The bulk density of the carbon nanotube array 91 is obtained by dividing the mass (that is, the amount of grain) of the carbon nanotube array 91 per unit area by the thickness of the carbon nanotube array 91.

FIG. 3 is a diagram showing the relationship between the bulk density of the carbon nanotube array 91 and the thickness of the carbon nanotube array 91. The circles in FIG. 3 are the conditions of the carbon nanotube array 91 in which the carbon nanotube wires could be particularly preferably formed in step S15 described later. Assuming that the bulk density of the carbon nanotube array 91 is D (mg / cm ³ ) and the thickness of the carbon nanotube array 91 is L (μm), it is preferable that ^{D ≧ 300 × L −0.5.} The curve in FIG. 3 shows D = 300 × L ^−0.5 .

In the example shown in FIG. 1, the substrate holding portion 21 has a substantially cylindrical shape or a substantially cylindrical shape centered on a rotation axis J1 extending in a direction perpendicular to the paper surface. The rotary shaft J1 is fixed to a frame or the like (not shown) of the molded body manufacturing apparatus 1. The substrate holding portion 21 holds the substrate 92 by abutting the back surface 922 of the substrate 92 from below. The back surface 922 of the substrate 92 is in contact with the outer surface of the substrate holding portion 21, for example, from the upper end portion to the right end portion of the substrate holding portion 21. The tip of the substrate 92 is wound around a substantially cylindrical or substantially cylindrical substrate take-up roll 231 arranged below the substrate holding portion 21.

The substrate take-up roll 231 is rotated clockwise in FIG. 1 by a rotation mechanism 232 about a rotation axis J2 extending in a direction perpendicular to the paper surface in FIG. The rotation shaft J2 is fixed to the above-mentioned frame or the like. Further, the substrate holding portion 21 rotates clockwise in FIG. 1 as the substrate take-up roll 231 rotates (for example, synchronously). As a result, the substrate 92 is wound around the substrate take-up roll 231, and the substrate 92 moves in the direction from the left side to the right side in FIG. 1 in the vicinity of the upper end portion of the substrate holding portion 21. In the molded body manufacturing apparatus 1, the substrate winding roll 231 may be omitted, and the substrate 92 may be wound by the substrate holding portion 21 rotated by the rotation mechanism 232.

In the following description, the moving direction of the substrate 92 in the vicinity of the upper end portion of the substrate holding portion 21 is referred to as a “board moving direction”, and is indicated by an arrow with reference numeral A1 in FIG. The substrate moving direction A1 is substantially vertical in the vertical direction. Further, in the following description, the direction perpendicular to both the vertical direction and the substrate moving direction A1 (that is, the direction perpendicular to the paper surface in FIG. 1 and the vertical direction in FIG. 2) is referred to as a "width direction". The width direction is also the width direction of the carbon nanotube array 91 and the width direction of the peeling array portion 93 described later.

The peeling member 22 is arranged near the upper end portion of the substrate holding portion 21. The peeling member 22 is fixed to the above-mentioned frame or the like. The shape of the peeling member 22 in a side view is, for example, a substantially wedge shape or a substantially flat plate shape. In the example shown in FIG. 1, the peeling member 22 is a substantially wedge-shaped member in which the thickness of the left end portion is smaller than the thickness of the right end portion. The upper surface of the peeling member 22 is, for example, an inclined surface that goes upward toward the right side in FIG.

The left end (that is, the edge) of the peeling member 22 is the carbon standing on the substrate 92 at the joint between the carbon nanotube array 91 and the substrate 92 above the upper end of the substrate holding portion 21. It abuts on the lower end of the nanotube array 91). The width of the peeling member 22 in the width direction is larger than the width of the carbon nanotube array 91 in the width direction. The peeling member 22 comes into contact with the joint portion between the carbon nanotube array 91 and the substrate 92 over the entire width of the carbon nanotube array 91. The peeling member 22 may abut on the joint portion between the carbon nanotube array 91 and the substrate 92 only in a part of the carbon nanotube array 91 in the width direction.

In the vicinity of the upper end portion of the substrate holding portion 21, the substrate 92 is moved in the substrate moving direction A1 by the moving mechanism 23, so that the portion of the carbon nanotube array 91 that abuts on the edge portion of the peeling member 22 is the surface of the substrate 92. It is peeled off from 921. That is, the peeling member 22 and the moving mechanism 23 are included in the peeling mechanism 20 that peels the carbon nanotube array 91 from the substrate 92. Of the carbon nanotube array 91, the portion peeled from the substrate 92 is referred to as a “peeling array portion 93”. In FIG. 2, parallel diagonal lines are provided on the carbon nanotube array 91 and the peeling array portion 93. When the carbon nanotube array 91 is peeled off, the substrate 92 does not necessarily have to move, and the peeling member 22 may move along the surface 921 of the fixed substrate 92, as will be described later. In other words, the carbon nanotube array 91 is peeled from the substrate 92 by moving the peeling member 22 relative to the substrate 92.

The peeling array portion 93 peeled from the substrate 92 is moved away from the upper end portion of the substrate holding portion 21 on the right side in FIG. 1 along the upper surface of the peeling member 22 as the substrate 92 moves by the moving mechanism 23. ), And reaches the guide portion 24 arranged adjacent to the peeling member 22. The guide portion 24 is located diagonally to the upper right of the substrate holding portion 21 in FIG. The guide portion 24 is arranged below the peeling array portion 93 at a position along the moving path of the peeling array portion 93, and comes into contact with the lower surface of the peeling array portion 93. Above the guide portion 24, the suction portion 61 is arranged adjacent to the guide portion 24 with a slight gap. The suction portion 61 contacts the upper surface of the peeling array portion 93 located on the guide portion 24, and electrostatically sucks the peeling array portion 93. In other words, the suction portion 61 is arranged so as to face the guide portion 24 in the vertical direction with the peeling array portion 93 interposed therebetween at a position along the moving path of the peeling array portion 93, and the moving peeling array portion 93 is statically charged. Electrostatic adsorption.

In the following description, the moving direction of the peeling array portion 93 from the peeling member 22 to the guide portion 24 is referred to as "peeling portion moving direction A2". The peeling portion moving direction A2 is inclined from the substrate moving direction A1 toward the upper side (that is, the upper surface side of the peeling array portion 93) in the side view. The angle formed by the peeling portion moving direction A2 and the substrate moving direction A1 is, for example, 5 degrees to 10 degrees. The peeling portion moving direction A2 is also inclined with respect to the vertical direction. Further, the peeling portion moving direction A2 is perpendicular to the width direction. When the moving direction of the peeling array portion 93 immediately after being peeled from the substrate 92 is called the “peeling direction”, in the example shown in FIG. 1, the peeling direction is the same as the peeling portion moving direction A2.

FIG. 4 is a front view of the guide portion 24 and the suction portion 61 as viewed from the right side in FIG. In FIG. 4, the peeling array portion 93 located between the guide portion 24 and the suction portion 61 in the vertical direction is also shown. The guide portion 24 is a substantially cylindrical or substantially cylindrical member centered on the rotation axis J3 extending in the width direction. The guide unit 24 rotates clockwise in FIG. 1 around the rotation shaft J3 by a drive source such as a motor (not shown). The rotation shaft J3 is fixed to the above-mentioned frame or the like. The outer surface of the guide portion 24 is a guide surface 241 that contacts the lower surface of the peeling array portion 93 and guides the peeling array portion 93. In the example shown in FIG. 4, the guide portion 24 is a substantially drum-shaped member. In other words, the diameter of the guide portion 24 gradually decreases from both end portions in the width direction toward the center portion. The guide surface 241 is a curved surface extending in the width direction. Specifically, the guide surface 241 is a concave surface that is recessed in the central portion in the width direction from both ends in the width direction.

The suction portion 61 is a substantially cylindrical or substantially cylindrical member centered on the rotation axis J6 extending in the width direction. The suction unit 61 rotates counterclockwise in FIG. 1 around the rotation shaft J6 by a drive source such as a motor (not shown). The rotation shaft J6 is fixed to the above-mentioned frame or the like. The suction portion 61 is an electrostatic suction roll including a substantially cylindrical or substantially cylindrical suction portion main body 612 formed of an insulator and electrodes 613 arranged in a substantially cylindrical shape inside the suction portion main body 612. be.

The outer surface of the suction portion 61 (that is, the outer surface of the suction portion main body 612) is a suction surface 611 that is in contact with the upper surface of the peeling array portion 93 to guide the peeling array portion 93 and electrostatically suck the peeling array portion 93. In the example shown in FIG. 4, the suction portion 61 is a substantially barrel-shaped member. In other words, the diameter of the suction portion 61 gradually increases from both end portions in the width direction toward the center portion. The suction surface 611 is a curved surface extending in the width direction. Specifically, the suction surface 611 is a convex surface that is more convex than both ends in the width direction at the central portion in the width direction. The suction surface 611 is substantially parallel to the guide surface 241 at a position facing the guide portion 24 in the vertical direction. In other words, at the position where the suction portion 61 and the guide portion 24 face each other in the vertical direction, the gap between the suction surface 611 and the guide surface 241 is substantially the same in the overall length in the width direction. The suction surface 611 and the guide surface 241 do not necessarily have to be convex and concave, and may be, for example, substantially cylindrical surfaces centered on the rotation axes J6 and J3.

In the suction unit 61, a voltage is applied to the electrode 613 in the suction unit main body 612, so that a Coulomb force is generated between the electrode 613 and the peeling array unit 93, which is the object of adsorption. Then, due to the Coulomb force, a portion of the peeling array portion 93 located between the suction portion 61 and the guide portion 24 (that is, the tip portion of the peeling array portion 93) is electrostatically charged to the suction surface 611 of the suction portion 61. Be adsorbed. The peeling array portion 93 is guided from the peeling portion moving direction A2 to the drawing direction A3 in a state of being electrostatically attracted by the suction portion 61.

The suction force of the peeling array unit 93 by the suction unit 61 is appropriately set within a range that does not hinder the withdrawal of the carbon nanotube sheet 94 from the peeling array unit 93, which will be described later. The attraction force (i.e., the gripping force) is, for ^{example, 0.1mg / cm 2 ~10mg / cm 2} , ^{preferably, 0.5mg / cm 2 ~5mg / cm} 2.

In the suction unit 61, the electrode 613 may be provided inside the suction unit main body 612 independently of the suction unit main body 612. In this case, the electrode 613 has, for example, a rod shape extending in the width direction, and is arranged near the lower end portion of the suction portion main body 612 regardless of whether the suction portion main body 612 is rotated or stopped. Then, when a voltage is applied to the electrode 613, the upper surface of the peeling array portion 93 that comes into contact with the lower end portion of the suction portion main body 612 is electrostatically attracted to the suction portion 61.

The peeling array portion 93 that reaches the upper end portion of the guide portion 24 and is electrostatically attracted by the suction portion 61 is pulled out in the predetermined pull-out direction A3 by the pull-out mechanism 26. As a result, the carbon nanotube sheet 94 extending in the drawing direction A3 of the peeling array portion 93 is formed. The carbon nanotube sheet 94 extends in the width direction of the peeling array portion 93. In the example shown in FIG. 2, the carbon nanotube sheet 94 has a shape in which a substantially triangular portion is continuous on the front side of the drawing direction A3 of the substantially rectangular portion. The shape of the carbon nanotube sheet 94 may be changed in various ways, and may be, for example, a substantially triangular shape in which the width in the width direction gradually decreases as the distance from the guide portion 24 in the drawing direction A3 increases. The carbon nanotube sheet 94 may have a flat substantially triangular shape in which the length in the drawing direction A3 is very small as compared with the width in the width direction.

The carbon nanotube sheet 94 is a sheet-shaped carbon nanotube molded body formed of a plurality of carbon nanotubes. Specifically, in the carbon nanotube sheet 94, a plurality of carbon nanotube single threads drawn out from the peeling array portion 93 in the drawing direction A3 are arranged in the width direction and connected to each other to form a sheet-like molded body (mesh-shaped molded body). It can also be regarded as). The single-walled carbon nanotube is a linear carbon nanotube molded body in which a plurality of carbon nanotubes are continuously connected in the longitudinal direction by a van der Waals force or the like.

The above-mentioned pull-out direction A3 is inclined from the peeling portion moving direction A2 toward the lower side (that is, the lower surface side of the peeling array portion 93) in the side view. In other words, the pull-out direction A3 is inclined downward from the virtual surface including the upper surface of the peeling array portion 93 (that is, the virtual plane parallel to the peeling portion moving direction A2 and the width direction). In the molded body manufacturing apparatus 1, the guide portion 24 has a structure that limits the moving direction of the peeling array portion 93 and guides the peeling array portion 93 to the drawing direction A3 that is inclined with respect to the peeling portion moving direction A2. The absolute value of the angle α formed by the pull-out direction A3 and the peeling portion moving direction A2 is, for example, larger than 0 degrees and 45 degrees or less. The absolute value of the angle α is preferably 30 degrees or less, more preferably 20 degrees or less. In the example shown in FIG. 1, the pull-out direction A3 is perpendicular to the width direction. Further, in the example shown in FIG. 1, the drawing direction A3 is substantially parallel to the substrate moving direction A1.

In the molded body manufacturing apparatus 1, the carbon nanotube array 91 is peeled from the substrate 92 and then the carbon nanotube sheet 94 is pulled out so that the carbon nanotube array 91 on the substrate 92 has pinholes, or the substrate 92. Even when the carbon nanotube array 91 above contains foreign matter, partial defects in the carbon nanotube sheet 94 can be suppressed. Specifically, since the movement of the carbon nanotubes contained in the peeling array portion 93 is not restricted by the substrate 92, when the peeling array portion 93 has voids due to the above-mentioned pinholes or foreign substances, the periphery of the voids is present. The carbon nanotubes of the above move to fill the voids. Further, it is prevented that the carbon nanotubes located on the rear side of the gap moving portion moving direction A2 remain on the substrate 92 against the pulling force. As a result, in the carbon nanotube sheet 94 pulled out from the peeling array portion 93, the occurrence of partial defects due to the voids is suppressed.

The carbon nanotube sheet 94 pulled out from the peeling array portion 93 passes through the wire forming portion 25. In the wire forming portion 25, the carbon nanotube wire 95 is formed by collecting the carbon nanotube sheets 94 in the width direction. The carbon nanotube wire 95 is a linear carbon nanotube molded body formed of a plurality of carbon nanotubes. In the wire forming portion 25, the carbon nanotube sheets 94 are collected toward the central portion in the width direction, and a large number of carbon nanotubes are brought into close contact with each other in the width direction.

In the example shown in FIG. 1, the wire forming portion 25 is a twisting machine that forms a carbon nanotube wire 95 by twisting a plurality of carbon nanotube single yarns of a carbon nanotube sheet 94 collected in the width direction. That is, the carbon nanotube wire 95, which is a carbon nanotube twisted yarn, is formed by twisting the carbon nanotube molded bodies collected in a substantially linear shape before passing through the wire forming portion 25 by the wire forming portion 25. In other words, the carbon nanotube sheet 94 is a precursor of the carbon nanotube wire 95.

After passing through the wire forming portion 25, the carbon nanotube wire 95 is wound on the molded body winding roll 261 rotated by the rotating mechanism 262 in the drawing mechanism 26. The molded body take-up roll 261 is a substantially cylindrical or substantially cylindrical member arranged on the right side of the wire forming portion 25. The molded body take-up roll 261 is rotated clockwise in FIG. 1 about a rotation axis J4 extending in the width direction. The rotation shaft J4 is fixed to the above-mentioned frame or the like.

FIG. 5 is a diagram showing a flow of manufacturing a carbon nanotube molded body by the molded body manufacturing apparatus 1. In the production of the carbon nanotube molded body, first, a carbon nanotube array 91, which is an assembly of carbon nanotubes erected on the substrate 92, is prepared (step S11). Subsequently, the carbon nanotube array 91 is peeled off from the substrate 92 (step S12). Next, the carbon nanotube array 91 (that is, the peeled array portion 93) peeled from the substrate 92 is electrostatically adsorbed by the suction portion 61 (step S13). After that, the carbon nanotube sheet 94 is formed by pulling out the carbon nanotube array 91 in a state of being electrostatically adsorbed on the adsorption portion 61 (step S14).

By performing the above steps S11 to S14, vibration in the width direction of the carbon nanotube array 91 at the time of drawing can be suppressed. Specifically, the tip end portion of the carbon nanotube array 91 peeled from the substrate 92 (that is, the tip end portion of the peeling array portion 93) is electrostatically adsorbed by the suction portion 61, so that the tip portion can be moved in the width direction. Movement is restricted. As a result, when the carbon nanotubes are pulled out from the tip of the peeling array portion 93, the position of the tip of the peeling array portion 93 in the width direction fluctuates (that is, the peeling array portion 93 vibrates in the width direction). It can be suppressed. Therefore, the carbon nanotube sheet 94 can be stably pulled out from the carbon nanotube array 91. As a result, in the carbon nanotube sheet 94, the uniformity of density can be improved over the entire width.

In order to perform the steps S11 to S14, the molded body manufacturing apparatus 1 illustrated in FIG. 1 includes a substrate holding portion 21, a peeling mechanism 20, a suction portion 61, and a drawing mechanism 26. The substrate holding portion 21 holds the substrate 92 on which the carbon nanotube array 91 is erected. The peeling mechanism 20 peels the carbon nanotube array 91 from the substrate 92. The adsorption unit 61 electrostatically adsorbs the carbon nanotube array 91 peeled off from the substrate 92. The extraction mechanism 26 forms the carbon nanotube sheet 94 by pulling out the carbon nanotube array 91 in a state of being electrostatically adsorbed by the adsorption portion 61. As a result, as described above, vibration in the width direction of the carbon nanotube array 91 at the time of drawing can be suppressed.

In the method for producing the carbon nanotube molded body described above, the linear carbon nanotube wire 95 is formed by collecting the carbon nanotube sheets 94 in the width direction after step S13 (step S15). In the manufacturing method, as described above, the vibration in the width direction of the carbon nanotube array 91 at the time of drawing can be suppressed, so that the carbon nanotube wire 95 can be stably formed. As a result, in the carbon nanotube wire 95, the uniformity of density in the longitudinal direction can be improved. As a result, it is possible to prevent breakage and cutting of the carbon nanotube wire 95 during manufacturing.

Preferably, in step S15, the carbon nanotube wire 95 is formed by twisting the carbon nanotube sheet 94. As a result, the high-density carbon nanotube wire 95 can be manufactured. As a result, the tensile strength of the carbon nanotube wire 95 can be improved.

In the method for producing the carbon nanotube molded product described above, preferably, in step S12, the peeling member 22 is brought into contact with the substrate 92 in a state where the peeling member 22 is in contact with the joint portion between the carbon nanotube array 91 and the substrate 92. Move relatively. As a result, the peeling array portion 93, which is a portion of the carbon nanotube array 91 that has been peeled from the substrate 92, is formed, and the peeling array portion 93 is relative to the peeling member 22 in the predetermined peeling portion moving direction A2. Moving. Further, in step S13, the peeling array portion 93 during relative movement is electrostatically attracted by the suction portion 61 arranged along the relative movement path of the peeling array portion 93. Further, in step S14, the carbon nanotube sheet 94 is pulled out from the peeling array portion 93 that is relatively moving in a state of being electrostatically adsorbed by the adsorption portion 61. As a result, the carbon nanotube sheet 94 can be continuously formed while suppressing the vibration of the peeling array portion 93 in the width direction.

More preferably, the drawing direction A3, which is the direction in which the carbon nanotube sheet 94 is pulled out, is a direction in which the carbon nanotube sheet 94 is inclined with respect to the peeling portion moving direction A2. As a result, the carbon nanotube sheet 94 can be suitably manufactured while suppressing the size of the molded body manufacturing apparatus 1 from increasing in size in the peeling portion moving direction A2.

As described above, the absolute value of the angle formed by the pull-out direction A3 and the peeling portion moving direction A2 is preferably 45 degrees or less. As a result, it is possible to prevent the tensile strength of the single-walled carbon nanotubes drawn from the peeling array portion 93 in the drawing direction A3 (that is, the connection strength between the carbon nanotubes in the single-walled carbon nanotubes) from becoming excessively small. As a result, breakage and cutting of the carbon nanotube sheet 94 and breakage and cutting of the carbon nanotube wire 95 during manufacturing can be more preferably prevented.

Further, the pull-out direction A3 is preferably inclined from the peeling portion moving direction A2 toward the lower surface side of the peeling array portion 93. In this case, the peeling array portion 93 that moves in the peeling portion moving direction A2 along the upper surface of the peeling member 22 is pulled out to the side supported by the peeling member 22. As a result, the carbon nanotube sheet 94 can be easily pulled out in the drawing direction A3 without providing a member for supporting the peeling array portion 93 separately from the peeling member 22. In addition, it is possible to prevent the molded body manufacturing apparatus 1 from becoming larger in the vertical direction.

As described above, in the production of the carbon nanotube sheet 94 and the carbon nanotube wire 95, ^{the relationship between the bulk density D (mg / cm 3} ) of the carbon nanotube array 91 and the thickness L (μm) of the carbon nanotube array 91 is determined. It is preferable that D ≧ 300 × L ^−0.5. As a result, the carbon nanotube sheet 94 and the carbon nanotube wire 95 can be suitably manufactured while preventing breakage and cutting during the production of the carbon nanotube sheet 94 and the carbon nanotube wire 95. The relationship between the bulk density D (mg / cm ³ ) and the thickness L (μm) of the carbon nanotube array 91 may be ^{D <300 × L −0.5.}

As described above, it is preferable that the molded body manufacturing apparatus 1 further includes a guide portion 24 arranged along the relative movement path of the peeling array portion 93. The guide unit 24 guides the peeling array unit 93 while rotating around the rotation axis J3 perpendicular to the relative movement path. Further, it is preferable that the suction portion 61 is arranged at a position facing the guide portion 24 with the peeling array portion 93 interposed therebetween. By sandwiching the tip of the peeling array portion 93 between the guide portion 24 and the suction portion 61 from above and below in this way, vibration in the width direction of the carbon nanotube array 91 at the time of pulling out can be further suppressed.

As described above, the guide portion 24 includes a guide surface 241 extending in the width direction and in contact with the peeling array portion 93. The guide surface 241 is preferably a concave surface that is recessed in the central portion in the width direction rather than both ends in the width direction. As a result, it is possible to prevent the carbon nanotubes located on the guide portion 24 from moving outward in the width direction. As a result, the vibration of the carbon nanotube array 91 in the width direction at the time of drawing can be further suppressed.

FIG. 6 is a side view showing the molded product manufacturing apparatus 1a according to the second embodiment of the present invention. The molded body manufacturing apparatus 1a has substantially the same structure as the molded article manufacturing apparatus 1 shown in FIG. 1 except that the suction portion 61a is provided in place of the guide portion 24 and the suction portion 61 described above. In the following description, among the configurations of the molded product manufacturing apparatus 1a, those corresponding to the configurations of the molded product manufacturing apparatus 1 are designated by the same reference numerals. The flow of manufacturing the carbon nanotube molded body by the molded body manufacturing apparatus 1a is substantially the same as that shown in FIG.

FIG. 7 is a front view of the suction portion 61a as viewed from the right side in FIG. In FIG. 7, the peeling array portion 93 located on the suction portion 61a is also shown. The suction portion 61a is arranged at substantially the same position as the guide portion 24 in FIG. The suction portion 61a is a substantially cylindrical or substantially cylindrical member centered on the rotation axis J6 extending in the width direction. The suction portion 61a is rotated clockwise in FIG. 1 around the rotation shaft J6 by a drive source such as a motor (not shown). The rotation shaft J6 is fixed to the above-mentioned frame or the like. The suction portion 61a is an electrostatic suction roll including a substantially cylindrical or substantially cylindrical suction portion main body 612a formed of an insulator and electrodes 613a arranged in a substantially cylindrical shape inside the suction portion main body 612a. be.

The suction surface 611a, which is the outer surface of the suction portion 61a, is also a guide surface that comes into contact with the lower surface of the peeling array portion 93 and guides the peeling array portion 93. In the example shown in FIG. 7, the suction portion 61a has substantially the same shape as the substantially drum-shaped guide portion 24 described above. The diameter of the suction portion 61a gradually decreases from both end portions in the width direction toward the center portion. The suction surface 611a is a curved surface extending in the width direction. Specifically, the suction surface 611a is a concave surface that is recessed in the central portion in the width direction from both ends in the width direction.

In the suction portion 61a, a voltage is applied to the electrode 613a in the suction portion main body 612a, so that a Coulomb force is generated between the electrode 613a and the peeling array portion 93 which is the object to be sucked. Then, due to the Coulomb force, a portion of the peeling array portion 93 located on the suction portion 61a (that is, the tip portion of the peeling array portion 93) is electrostatically attracted to the suction surface 611a of the suction portion 61a. The peeling array portion 93 is guided from the above-mentioned peeling portion moving direction A2 to the drawing direction A3 in a state of being electrostatically attracted by the suction portion 61a. The suction force of the peeling array section 93 by the suction section 61a is substantially the same as the suction force of the suction section 61 described above.

In the molded body manufacturing apparatus 1a, the peeling array portion 93 is electrostatically adsorbed by the adsorption portion 61a, so that vibration in the width direction of the carbon nanotube array 91 at the time of drawing can be suppressed in the same manner as described above. Further, the suction portion 61a is preferably a guide portion that guides the peeling array portion 93 while rotating about the rotation axis J6 perpendicular to the relative movement path of the peeling array portion 93. In this way, the structure of the molded body manufacturing apparatus 1a can be simplified by allowing the suction portion 61a to also serve as the guide portion for guiding the release array portion 93.

As described above, the suction portion 61a includes a suction surface 611a that extends in the width direction and is in contact with the peeling array portion 93. The suction surface 611a is preferably a concave surface that is recessed in the central portion in the width direction from both end portions in the width direction. As a result, it is possible to prevent the carbon nanotubes located on the adsorption portion 61a from moving outward in the width direction. As a result, the vibration of the carbon nanotube array 91 in the width direction at the time of drawing can be further suppressed.

In the suction unit 61a, the electrode 613a may be provided inside the suction unit main body 612a independently of the suction unit main body 612a. In this case, the electrode 613a has, for example, a rod shape extending in the width direction, and is arranged near the upper end portion of the suction portion main body 612a regardless of whether the suction portion main body 612a is rotated or stopped. Then, when a voltage is applied to the electrode 613a, the lower surface of the peeling array portion 93 that comes into contact with the upper end portion of the suction portion main body 612a is electrostatically attracted to the suction portion 61a.

FIG. 8 is a side view of the molded product manufacturing apparatus 1b according to the third embodiment of the present invention. In the molded body manufacturing apparatus 1b, a moving mechanism 23b for moving the peeling member 22 is provided instead of the moving mechanism 23 (see FIG. 1) for moving the substrate 92. In the molded body manufacturing apparatus 1b, the peeling member 22 moves from the right side to the left side in the drawing along the surface 921 of the substrate 92 which is held on the base 10 and does not move. As the peeling member 22 moves relative to the substrate 92 in this way, the carbon nanotube array 91 is peeled from the substrate 92.

In the example shown in FIG. 8, the moving mechanism 23b is a linear guide mechanism including a guide rail 233 fixed above the peeling member 22 and a ball screw and a motor (not shown). The structure of the moving mechanism 23b may be changed in various ways. Further, in the example shown in FIG. 8, the peeling member 22 is connected to the guide portion 24, the wire forming portion 25, the pull-out mechanism 26, and the suction portion 61b via the support member 234. The guide portion 24 is arranged along the relative movement path of the peeling array portion 93 in the same manner as described above, and guides the peeling array portion 93. The suction portion 61b has substantially the same structure as the above-mentioned suction portion 61, and is arranged at a position facing the guide portion 24 with the peeling array portion 93 interposed therebetween. The suction unit 61b electrostatically sucks the peeling array unit 93. Thereby, similarly to the above, the vibration in the width direction of the carbon nanotube array 91 at the time of drawing can be suppressed.

In the molded body manufacturing apparatus 1b, the peeling member 22, the guide portion 24, the wire forming portion 25, the pull-out mechanism 26, and the suction portion 61b are integrally moved by the moving mechanism 23b. Therefore, since the relative positions of the peeling member 22, the guide portion 24, the wire forming portion 25, the pull-out mechanism 26, and the suction portion 61b are fixed, it is possible to simplify the control of the pull-out speed and the like by the pull-out mechanism 26. As a result, the carbon nanotube molded body (that is, the carbon nanotube sheet 94 and the carbon nanotube wire 95) can be preferably formed.

Various changes can be made in the above-mentioned molded product manufacturing apparatus 1, 1a, 1b and the method for manufacturing the carbon nanotube molded product.

For example, the suction portion 61 does not necessarily have to be substantially cylindrical or substantially cylindrical, and does not need to rotate. The suction portion 61 may be, for example, a flat plate-shaped member having a flat suction surface 611. The same applies to the suction portions 61a and 61b.

The guide portion 24 does not necessarily have to be substantially cylindrical or substantially cylindrical, and does not need to rotate. Further, the guide portion 24 may be a member that is connected to the peeling member 22. Alternatively, the guide unit 24 may be omitted.

In the peeling member 22, ultrasonic vibration may be applied to the edge portion in contact with the carbon nanotube array 91. This makes it possible to easily peel the carbon nanotube array 91 from the substrate 92.

In the production of the carbon nanotube molded body described above, the drawing direction A3 may be inclined from the peeling portion moving direction A2 toward the upper side (that is, the upper surface side of the peeling array portion 93) in the side view. In other words, the pull-out direction A3 may be inclined upward from the virtual surface including the lower surface of the peeling array portion 93 (that is, the virtual surface parallel to the peeling portion moving direction A2 and the width direction). Further, the absolute value of the angle formed by the pull-out direction A3 and the peeling portion moving direction A2 may be larger than 45 degrees. Alternatively, the pull-out direction A3 may be parallel to the peeling portion moving direction A2. The pull-out direction A3 does not necessarily have to be perpendicular to the width direction, and may be inclined to one side in the width direction.

In the production of the carbon nanotube molded body described above, it is not always necessary to pull out the carbon nanotube sheet 94 from the peeling array portion 93 that is moving relative to the peeling member 22, and the carbon nanotube sheet 94 is not necessarily pulled out from the peeling array portion 93 in the stationary state. May be pulled out. For example, as shown in FIG. 9, the carbon nanotube array 91 peeled off from the substrate by another device (not shown) is stationary in a state of being electrostatically adsorbed by the substantially flat adsorption portion 61c, and the carbon is said. The carbon nanotube sheet 94 may be pulled out from the nanotube array 91, and the carbon nanotube wire 95 may be formed by the wire forming portion 25.

In the molded body manufacturing apparatus 1 of FIG. 1, an example in which the wire forming portion 25 and the drawing mechanism 26 are individually provided is shown, but even if the wire forming portion 25 and the drawing mechanism 26 are included in one mechanism. good. The one mechanism is, for example, a mechanism for winding the carbon nanotube sheet 94 while twisting it linearly. The same applies to the molded body manufacturing devices 1a and 1b.

The carbon nanotube wire 95 formed by the molded body manufacturing apparatus 1 does not necessarily have to be a carbon nanotube twisted yarn, and may be an untwisted carbon nanotube untwisted yarn. In this case, the wire forming portion 25 may be, for example, a mechanism for performing a process (so-called Taslan process) of blowing compressed air on a plurality of carbon nanotube single yarns contained in the carbon nanotube sheet 94 to bind them. Alternatively, the wire forming portion 25 may be a die provided with pores for forming the carbon nanotube wire 95 by passing a plurality of carbon nanotube single threads. The same applies to the molded body manufacturing devices 1a and 1b.

In the molded body manufacturing apparatus 1, the wire forming portion 25 may be omitted, and the substantially rectangular carbon nanotube sheet 94 may be manufactured as a carbon nanotube molded body. The same applies to the molded body manufacturing devices 1a and 1b.

The above-described embodiment and the configurations in each modification may be appropriately combined as long as they do not conflict with each other.

1,1a, 1b Carbon nanotube molded body manufacturing equipment 20 Peeling mechanism 21 Substrate holding part 22 Peeling member 23,23b Moving mechanism 24 Guide part 25 Wire forming part 26 Pulling mechanism 61, 61a to 61c Adsorption part 91 Carbon nanotube array 92 Substrate 93 Peeling array part 94 Carbon nanotube sheet 95 Carbon nanotube wire A2 Peeling part Moving direction A3 Pulling direction J3, J6 Rotation axis S11-S15 Step

Claims (12)

It is a method for manufacturing carbon nanotube molded products.
a) The process of preparing a carbon nanotube array, which is a collection of carbon nanotubes erected on a substrate, and
b) A step of peeling the carbon nanotube array from the substrate and
c) A step of electrostatically adsorbing the carbon nanotube array peeled from the substrate by an adsorption part, and
d) A step of forming a carbon nanotube sheet by pulling out the carbon nanotube array in a state of being electrostatically adsorbed on the adsorption portion.
A method for producing a carbon nanotube molded product, which comprises the above. The method for producing a carbon nanotube molded product according to claim 1.
In the step b), the peeling member is moved relative to the substrate in a state where the peeling member is in contact with the joint portion between the carbon nanotube array and the substrate, whereby the carbon nanotube array is subjected to. A peeling array portion, which is a portion peeled from the substrate, is formed and moves relative to the peeling member in a predetermined peeling portion moving direction.
In the step c), the peeling array portion during relative movement is electrostatically adsorbed by the suction portion arranged along the relative movement path of the peeling array portion.
A method for producing a carbon nanotube molded body, which comprises pulling out the carbon nanotube sheet from the peeling array portion which is relatively moving in a state of being electrostatically adsorbed by the adsorption portion in the step d). The method for producing a carbon nanotube molded product according to claim 2.
A method for producing a carbon nanotube molded body, wherein the drawing direction, which is the drawing direction of the carbon nanotube sheet, is a direction inclined with respect to the moving direction of the peeled portion. The method for producing a carbon nanotube molded product according to any one of claims 1 to 3.
e) A method for producing a carbon nanotube molded body, further comprising a step of forming linear carbon nanotube wires by collecting the carbon nanotube sheets in the width direction after the step d). The method for producing a carbon nanotube molded product according to claim 4.
A method for producing a carbon nanotube molded body, which comprises forming the carbon nanotube wire by twisting the carbon nanotube sheet in the step e). It is a carbon nanotube molded product manufacturing equipment.
A substrate holding part that holds a substrate on which a carbon nanotube array, which is a collection of carbon nanotubes, stands,
A peeling mechanism for peeling the carbon nanotube array from the substrate,
An adsorption part that electrostatically adsorbs the carbon nanotube array peeled off from the substrate,
A drawing mechanism for forming a carbon nanotube sheet by pulling out the carbon nanotube array in a state of being electrostatically adsorbed on the suction portion, and
A carbon nanotube molded product manufacturing apparatus, which comprises. The carbon nanotube molded product manufacturing apparatus according to claim 6.
The peeling mechanism is
A peeling member that comes into contact with the joint between the carbon nanotube array and the substrate,
By moving the peeling member relative to the substrate, a peeling array portion, which is a portion of the carbon nanotube array that has been peeled from the substrate, is formed, and the peeling array portion is attached to the peeling member. And a movement mechanism that moves relative to the predetermined peeling part movement direction,
With
The suction portion is arranged along the relative movement path of the peeling array portion, and electrostatically attracts the peeling array portion during relative movement.
The drawing mechanism is a carbon nanotube molded body manufacturing apparatus, characterized in that the carbon nanotube sheet is pulled out from the peeling array portion that is relatively moving in a state of being electrostatically adsorbed by the adsorption portion. The carbon nanotube molded product manufacturing apparatus according to claim 7.
A carbon nanotube molded body manufacturing apparatus , wherein the drawing direction, which is the drawing direction of the carbon nanotube sheet, is a direction inclined with respect to the moving direction of the peeled portion. The carbon nanotube molded product manufacturing apparatus according to claim 7 or 8.
A guide portion that is arranged along the relative movement path of the peeling array portion and guides the peeling array portion while rotating about a rotation axis perpendicular to the relative movement path is further provided.
A carbon nanotube molded product manufacturing apparatus, wherein the suction portion is arranged at a position facing the guide portion with the peeling array portion interposed therebetween. The carbon nanotube molded product manufacturing apparatus according to claim 7 or 8.
The carbon nanotube molded article manufacturing apparatus, wherein the suction portion is a guide portion that guides the peeling array portion while rotating about a rotation axis perpendicular to the relative movement path. The carbon nanotube molded product manufacturing apparatus according to any one of claims 6 to 10.
A carbon nanotube molded body manufacturing apparatus, further comprising a wire forming portion for forming linear carbon nanotube wires by collecting the carbon nanotube sheets in the width direction. The carbon nanotube molded product manufacturing apparatus according to claim 11.
The wire forming portion is a carbon nanotube molded body manufacturing apparatus, characterized in that the carbon nanotube wire is formed by twisting the carbon nanotube sheet.

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